IL118502A - 6-alkoxy methyl quinolines, process and intermediates for their preparation - Google Patents

6-alkoxy methyl quinolines, process and intermediates for their preparation

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Publication number
IL118502A
IL118502A IL11850296A IL11850296A IL118502A IL 118502 A IL118502 A IL 118502A IL 11850296 A IL11850296 A IL 11850296A IL 11850296 A IL11850296 A IL 11850296A IL 118502 A IL118502 A IL 118502A
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Israel
Prior art keywords
compound
branched
mixture
chlorine
alkyl straight
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IL11850296A
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IL118502A0 (en
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American Cyanamid Co
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Publication of IL118502A publication Critical patent/IL118502A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Quinoline Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

A compound of the formula wherein W, X and Y are independently H, halogen, NO2, NH2 or -O-alkyl straight or branched C1-C6, Z is H, halogen, NO2, NH2, OH or -O-alkyl straight or branched C1-C6 and B is chlorine, bromine, a quaternary ammonium halide or -O-alkyl straight or branched C1-C6; with the following provisos: (i) that when B is -O-alkyl straight or branched C1-C6; W is H; X is H and Y is H, then Z is not OH or -O-alkyl straight or branched C1-C5, (ii) that when B is - O-alkyl straight or branched C1-C6 ; Z is OH or -O-alkyl straight or branched C1-C6, then at least one of W, X and Y is selected from halogen, NO2 and NH2, and (iii) that when W, X, Y and Z are simultaneously H, then B is not chlorine. 58 ז' באייר התשס" א - April 30, 2001

Description

118502/3 ojittiiij o»i>i >ifcni t n» , νΉΜρ >:n& ^p)p n - 6 6-ALKOXY METHYL QUINOLINES, PROCESS AND INTERMEDIATES FOR THEIR PREPARATION PAT/4722 P/103/14722/146754/l Summary of the Invention The invention is substituted quinoline intermediates useful in the synthesis of the herbicide 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolidinyl) -5-methoxymethylnicotinic acid and a process for preparing herbicide intermediates 3 -alkoxymethyl substituted quinolines .
Detailed Description The invention is compounds of the formula "wherein W, X and Y are independently H, halogen, N02. NH2 or -O-alkyI straight or branched C C6; Z is H, halogen, NO2, NH2, OH or -O-alkyl straight or branched CrC6 and B is chlorine, bromine, a quaternary ammonium halide or -O-alkyl straight or branched C,-C3 with the following provisos: that when B is -O-alkyl straight or branched C C6, W is H; X is H and Y is K then Z is not OH or -O-alkyl straight or branched CpCe, that when B is -O-alkyl straight or branched Ci-C6; Z is OH or -O-alkyl straight or branched d-C6, then at least one of W. X and Y is selected from halogen, N02 and NH2, and that when W, X, Y and 2 are simultaneously H. then B is not chlorine. and a process for preparing compounds of the formula wherein W, X, Y, and Z are defined according to claim 1 , and R represents -O-alkyl straight or branched d-Ce, which comprises: reacting a compound of formula II wherein W, X, Y, and 2 are defined according to claim 1, with a radical halogenating reagent wherein the halogen is bromine or chlorine to form a compound of formula III wherein W, X, Y, and 2 are defined according to claim 1; reacting compound 111 with a tertiary amine to form a compound of formula IV 118502/3 - 3 - wherein W, X, Y, and 2 are defined according to claim 1 and B is a quaternary ammonium halide; and reacting compound IV with RM wherein R is as defined above and M is Na, Li, or .
The 3-alkoxymethyl substituted quinolines of the invention are herbicide intermediates useful in the synthesis of the substituted quinoline herbicide intermediates to the herbicide intermediate 5- methoxymethyl-2 , 3 -pyridinedicarboxylic acid for the herbicide 2- (4-iscpropyl-4-methyl-5-oxo-2- imidazclidinyl) -5-methoxymethylnicotinic acid of U.S. Patent 3,334,576 corresponding to EL 88663 The invention is further illustrated in the examples, below, but is not to be deemed limited thereb .
EXAMPLE 1 Preparation of - (Bromomethyl ) - 8 -nitroquinoline A stirred mixture of 3 -methyl - 8 -nitroquinoline (9.5 g, under nitrogen. A mixture of N-bromosuccinimide (9.0g 0.05 mol) . and 2 , 2 ' -azobisisobutyronitrile (0.5 g, 0.003 mol) is added to the reaction mixture. The reaction mixture is held at 80-90°C for 1 hour. The mixture is washed with water (100 mL) at 60-80°C , cooled to room temperature and filtered to obtained a solid. The. solid is washed with chlorobenzene and vacuum dried to give the title product as light -yellow solid (3.9 g mp 121-124°C) which is identified by Ε and 13C MR spectral analyses.
EXAMPLE 2 Preparation of (8-Nitro-3-quinolyl) methyltrimethyl-ammonium bromide A stirred mixture of 3-methyl-8-nitroquinoline (75 g, 0.40 mol) in chlorobenzene (1000 mL) is heated to 80°C under nitrogen. A mixture of N-bromosuccinimide (75g 0.42 mol). and 2 , 2 ' -azobisisobutyronitrile (4 g, 0.024 mol) is added to the reaction mixture over 30 minutes at 80-90°C. After the addition is complete, the reaction mixture is held a 80-90°C for 4 hours. The mixture is washed with water (400 mL) at 60-80°C and the crganic mixture is diluted with acetone (300 mL) .
The mixture is cooled to 10°C and anhydrous rime hylamine '45 g, 0.33 ci) is added. The mixture is stirred overnight at 10-30°C and filtered to obtained a solid. The solid is washed with acetone and vacuum dried to give the title product as light -yellow solid (74.0 g) which is identified by and iJC MR spectral analyses.
EXAMPLE 3 Preparation of 3- (Methcxymethyl) -8-nitroquinoline A mixture of 25% sodium methoxide ( 88 g, 0.19 moi) in methanol (600 mL) and (8-nitro-3 -quinciyi) methyitrimethyiammonium bromide (63 g, 0.19 mol) is heated under nitrogen at reflux for 2 hours and cooled to room temperature. The resulting mixture is diluted with ice water (600 mL) and filtered to obtaine a solid. The solid is washed with water and vacuum dried to give the title product as an off-white solid (32.2 g, tr.p 69-71°C} which is identified by and 13C NMR spectral analyses.
EXAMPLE 4 Preparation of 3- ( ethoxymethyl) -8-aminoquinol A mixture of 3- (methoxymethyl) -8-nitroquinoline (5.64g 0.026 mol) , 5% palladium on carbon (0.32g) and methanol (70 mL) in a pressure vessel is heated to 45°C. The mixture is treated with hydrogen at 30 psig for 4 hours at 45°C and cooled to room temperature.
The mixture is filtered to remove the palladium on carbon and the cake is washed with methanol. The combined filtrate and wash is concentrated in vacuo to obtain the title product as a clear liquid (4.7 g) which is identified by 1H and 13C NMR spectral analyses .
EXAMPLE 5 Preparation of 3- (Bromomethyl) -8-chloroquinoline A stirred mixture of 3 -methyl -8-chloroquinoline (9 05 mol) in chlorobenzene (75 mL) is heated to 80°C under nitrogen. A mixture of N-bromosuccinimide (9.0g 0.05 mol) . and 2 , 21 -azobisisobutyronitrile (0.5 g, 0.003 mol) is added to the reaction mixture. The reaction mixture is held a 80-90°C for 1 hour. The mixture is washed twice with water (50 mL) at 60-80°C and cooled to room temperature. The mixture is diluted with heptane (75 mL) and filtered to obtained a solid which is washed with chlorobenzene and then with heptane. The solid is vacuum dried to give the title product as an off-white solid (6.2 g, mp 125-129°C) which is identified by and NMR spectral analyses .
EXAMPLE 6 Preparation of (8-Chloro-3-quinolyl) methyltrimethyl- ammonium bromide A stirred mixture of 3-methyl-8-chloroquinoline (71.2 g, 0.4 mol) in chlorobenzene (700 mL) is heated to 80°C under nitrogen. A mixture of N-bromosuccinimide (71.2g, 0.4 mol). and 2 , 2 ' -azobisisobutyronitrile (4 g, 0.024 mol) is added to the reaction mixture over 30 minutes at 80-90°C. After the addition is complete, the reacjtion mixture is held a 80-90°C for 1.5 hours. The mixture is washed twice with water (300 mL) at 60-80°C and the organic mixture is diluted with acetone (250 mL) . The mixture is cooled to 10°C and anhydrous trimethylamine (29.5g, 0.5 mol) is added. The mixture is stirred at 10-30°C for 3 hours and filtered to obtained a solid. The solid is washed with acetone and vacuum dried to give the title product as an off-white solid (69.4 g) which is identified by l-H and 13C,NMR spectral analyses.
EXAMPLE 7 Preparation of 3- (Methoxymethyl) -8-chloroquinoline A mixture of 25% sodium methoxide(66 g, 0.3 mol) in methanol (600 mL) and (8-chloro-3-quinolyl) methyltrimethylammonium bromide (66 g, 0.21 mol) is heated under nitrogen at reflux for 3 hours and cooled to room temperature. The resulting mixture is diluted with ice water (500 mL) and extracted twice with methylene chloride (200 mL) . The extracts are combined, washed with water, and concentrated in vacuo to obtain the title product as a clear liquid (39.4 g) which is identified by ^-K and 13C N R spectral analyses .
EXAMPLE 8 Preparation of 3 - (Methoxymethyl) chloroquinoline 3- (Methoxymethyl) -8 -chloroquinoline (10.3g, 0.05 mol) is added to 96% sulfuric acid (40 g, 0.39 mol) at 10- 30°C and 70% nitric acid is then added over 15 minutes. The reaction mixture is stirred at room temperature for 14 hours, diluted with ice water ( 150 mL) and filtered to obtain a solid. The solid is washed with water and vacuum dried to give the title product as a yellow solid (9.4 g, mp 83-86°C) which is identified by Ε and !3c NMR spectral analyses.
EXAMPLE 9 Preparation of (7, 8-Dichloro-3-quinolyl] methyltrimethylammonium bromide A stirred mixture of 3 -methyl-7, 8-dichloroquinoline (106 g, 0.5 mol) in chlorobenzene (1000 mL) is heated to 80°C under nitrogen. A mixture of N-bromosuccinimide ( 89 g 0.5 mol). and 2 , 21 -azobisisobutyronitrile (3 g, 0.02 mol) is added to the reaction mixture over 30 minutes at 80-90°C. After the addition is complete, the reaction mixture is held a 80-90°C for 2 hours. The mixture is washed with water (400 mL) at 60-80°C and the organic mixture is diluted with acetone (300 mL) .
The mixture is cooled to 10°C and anhydrous trimethylamine (49 g, 0.83 mol) is added. The mixture is stirred overnight at 10-30°C and filtered to obtained a solid. The solid is washed with acetone and vacuum dried to give the title product as a white solid (129 g) which is identified by 1H and 13C MR spectral analyses .
EXAMPLE 10 Preparation of 3- (Methoxymethyl) -7, 8-dichloroquinoline A mixture of 25% sodium methoxide ( lOOg, 0.46 mol) in methanol (800 mL) and (7, 8-dichloro-3-quinolyl) methyltrimethylammonium bromide (110 g, 0.31 mol) is heated under nitrogen at reflux for 2 hours and cooled to room temperature. The resulting mixture is diluted with ice water (800 mL) and filtered to obtained a solid. The solid is washed with water and vacuum dried to give the title product as an off-white solid (64.30 g, ) which is identified by ^-H and 13C NMR spectral analyses .
EXAMPLE 11 Preparation of (5, 8-Dichloro-3-quinolyl) methyltrimethylammonium bromide A stirred mixture of 3-methyl-5, 8-dichloroquinoline (143 g, 0.67 mol) in chlorobenzene (1000 mL) is heated to 80°C under nitrogen. A mixture of N-bromosuccinimide (120 g 0.67 mol). and 2 , 2 ' -azobisisobutyronitrile (5 g, 0.03 mol) is added to the reaction mixture over 30 minutes at 80-90°C. After the addition is complete, the reaction mixture is held a 80-90°C for 3 hours. The mixture is washed with water (600 mL) at 60-80°C and the organic mixture is diluted with acetone (200 mL) . The mixture is cooled to 10°C and anhydrous trimethylamine (65g, 1.1 mol) is added. The mixture is stirred overnight at 10-30°C and filtered to obtained a solid. The solid is washed with acetone and vacuum dried to give the title product as a white solid (174.6 g, °C) which is identified by ^-H and 13C NMR spectral analyses .
EXAMPLE 12 Preparation of 3- (Methoxymethyl) -5, 8-dichloroquinoline A mixture of 25% sodium methoxide (130g, 0.6 mol) in methanol (800 mL) and (5, 8-dichloro-3-quinolyl) methyltrimethylammonium bromide (146 g, 0.41 mol) is heated under nitrogen at reflux for 2 hours and cooled to room temperature. The resulting mixture is diluted with ice water (1200 mL) and filtered to obtained a solid. The solid is washed with water and vacuum dried to give the title product as a light-tan solid (91 g, mp 00-00°C) which is identified by ^-H and 13C R spectral analyses .
EXAMPLE 13 Preparation of (8-Chloro-3-quinolyl) methyltrimethylammonium bromide using 1, 3-dibromo-5, 5-dimethylhydantoin A stirred mixture of 3-methyl-8-chloroquinoline (71.2 g, 0.4 mol) in chlorobenzene (700 mL) is heated to 80°C under nitrogen. A mixture of 1,3 dibromo-5,5-dimethylhydantoin ( 57 g, 0.02 mol). and 2,2'-azobisisobutyronitrile (4 g, 0.024 mol) is added to the reaction mixture over 30 minutes at 80-90°C. After the addition is complete, the reaction mixture is held a 80-90°C for 1.5 hours. The mixture is washed twice with water (300 mL) at 60-80°C and the organic mixture is diluted with acetone (250 mL) . The mixture is cooled to 10°C and anhydrous trimethylamine (36g, 0.6 mol) is added. The mixture is stirred at 10-30°C for 3 hours and filtered to obtained a solid. The solid is washed with acetone and vacuum dried to give the title product as off-white solid (34. lg) which is identified by 1H and 13C.

Claims (11)

1 18502/3 15 What is claimed is:
1. A compound of the formula "wherein W. X and Y are independently H, halogen, N02. NH2 or -O-alkyl straight or branched C,-C6; Z is H, halogen, N02, NH2, OH or -O-alkyl straight or branched C,-C6 and B is chlorine, bromine, a quaternary ammonium halide or -O-alkyl straight or branched 0,-Cs; with the following provisos: i) that when B is -O-alkyl straight or branched C1TC6; W is H; X is H and Y is H. then Z is not OH or - O-alkyl straight or branched C.-C3, ii) that when B is - O-alkyl straight or branched C,-C6; Z is OH or -O-alkyl straight or branched C C , then at least one of W, X and Y is selected from halogen, NO: and NH2, and that when W, X, Y and Z are simultaneously H, then B is not chlorine.
2. A compound according to claim 1 wherein W . X and Y are each H , Z is chlorine and B is bromine, trimethyl ammonium bromide or methoxy.
3. A compound according to claim 1 wherein i_ « - c wo. and B is bromine , W , X and Y are each H , ■ Z ≤ wu: -rimethyl ammonium bromide or methoxy. 102287/2
4. . A compound according to claim 1 wherein W, X and Y are each H, Z is NH2 and BisMethoxy
5. A compound according to claim 1 wherein X and Y are H, W is N02, Z is chlorine and B is -0-CH3.
6. A compound according to claim 1 wherein X and W are H, Y and Z are chlorine and B is trimethylammonium bromide .
7. . A compound according to claim 1 wherein X and are H, Y and Z are chlorine and B is -OCH3.
8. . A compound according to claim 1 wherein X and Y are H, W and Z are chlorine and B is -OCH3 or trimethylammonium bromide .
9. A process for preparing a compound of the formula wherein W, X, Y, and Z are defined according to claim 1, and R represents -O-alkyI straight or branched CrCe, which comprises: reacting a compound of formula II wherein W, X, Y, and Z are defined according to claim 1, with a radical halogenating reagent wherein the halogen is bromine or chlorine to form a compound of formula III - 16- 102287/3 z wherein W, X, Y, and Z are defined according to claim 1; reacting compound III with a tertiary amine to form a compound of formula IV wherein W, X, Y, and 2 are defined according to claim 1 and B is a quaternary ammonium halide; and reacting compound IV with RM wherein R is as defined above and M is Na, Li, or . ■17- halogenating reagent wherein the halogen is bromine or chlorine to form a compound of the formula reacting compound III with a tertiary amine to form a compound of the formula wherein B is a tertiary ammonium halide; and reacting compound IV with ROM wherein R is alkyl straight or, branched C1-C6 and M is Na, Li or K to form the compound of formula I .
10. A process according to claim 9 wherein ROM is sodium methoxide .
11. A process according to claim 9 wherein the radical halogenating agent to form compound III is N-bromosuccinimide or 1, 3-dibromo-5, 5-dimethylhydantoin and the tertiary amine to form compound IV amine . AGENT FOR THE APPLICANT
IL11850296A 1995-06-05 1996-05-31 6-alkoxy methyl quinolines, process and intermediates for their preparation IL118502A (en)

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US08/464,192 US5625068A (en) 1995-06-05 1995-06-05 Substituted quinoline herbicide intermediates and process

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IL118502A0 IL118502A0 (en) 1996-09-12
IL118502A true IL118502A (en) 2001-04-30

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NZ314904A (en) * 1996-06-10 1998-06-26 American Cyanamid Co Preparation of a herbicidal [(5,6-dicarboxy-3-pyridyl)methyl]ammonium halide

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US3252858A (en) * 1963-08-09 1966-05-24 Phillips Petroleum Co Insect repellents and method of using
FR2488609A1 (en) * 1980-08-18 1982-02-19 Rhone Poulenc Ind NOVEL DERIVATIVES OF THIOFORMAMIDE, THEIR PREPARATION AND THE MEDICINAL PRODUCTS CONTAINING THEM
US5334576A (en) * 1986-07-28 1994-08-02 American Cyanamid Company 5 (and/or 6) substituted 2-(2-imidazolin-2-yl)nicotinic acids, esters and salts, useful as herbicidal agents and novel intermediates for the preparation of said nicotinic acids, esters and salts
IL84944A (en) * 1987-01-19 1992-02-16 Ici Plc Pharmaceutical compositions containing 1,2-dihydro-3h-indazolone derivatives,some new such compounds and their preparation
US4888427A (en) * 1987-04-07 1989-12-19 University Of Florida Amino acids containing dihydropyridine ring systems for site-specific delivery of peptides to the brain
US5281713A (en) * 1991-12-20 1994-01-25 American Cyanamid Company Process for the manufacture of 2-alkoxymethylacrolein

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AU712070B2 (en) 1999-10-28
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HU9601521D0 (en) 1996-07-29
HU223326B1 (en) 2004-06-28
AR002305A1 (en) 1998-03-11
CZ146396A3 (en) 1996-12-11
SK68296A3 (en) 1997-01-08
CZ288847B6 (en) 2001-09-12
HUP9601521A2 (en) 1997-03-28
AU5474596A (en) 1996-12-19
CA2178061A1 (en) 1996-12-06
US5625068A (en) 1997-04-29
JPH08337572A (en) 1996-12-24
IL118502A0 (en) 1996-09-12
RU2161605C2 (en) 2001-01-10
CN1138035A (en) 1996-12-18
TW326448B (en) 1998-02-11
HUP9601521A3 (en) 1998-06-29
UA48124C2 (en) 2002-08-15
ZA964566B (en) 1997-12-03
YU33396A (en) 1998-12-23
SG47148A1 (en) 1998-03-20
KR970001329A (en) 1997-01-24
EP0747361A1 (en) 1996-12-11

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